Lobana Tarlok S, Rekha Rekha, Butcher R J, Castineiras A, Bermejo E, Bharatam Prasad V
Department of Chemistry, Guru Nanak Dev University, Amritsar, India.
Inorg Chem. 2006 Feb 20;45(4):1535-42. doi: 10.1021/ic051018j.
Reactions of copper(I) halides with a series of thiosemicarbazone ligands (Htsc) in the presence of triphenylphosphine (Ph(3)P) in acetonitrile have yielded three types of complexes: (i) monomers, [CuX(eta1-S-Htsc)(Ph3P)2] [X, Htsc = I (1), Br (2), benzaldehyde thiosemicarbazone (Hbtsc); I (5), Br (6), Cl (7), pyridine-2-carbaldehyde thiosemicarbazone (Hpytsc)], (ii) halogen-bridged dimers, [Cu2(mu2-X)2(eta1-S-Htsc)2(Ph3P)2] [X, Htsc = Br (3), Hbtsc; I (8), furan-2-carbaldehyde thiosemicarbazone (Hftsc); I (11), thiophene-2-carbaldehyde thiosemicarbazone (Httsc)], and (iii) sulfur-bridged dimers, [Cu2X2(mu2-S-Htsc)2(Ph3P)2] [X, Htsc = Cl (4), Hbtsc; Br (9), Cl (10), pyrrole-2-carbaldehyde thiosemicarbazone (Hptsc); Br (12), Httsc]. All of these complexes have been characterized with the help of elemental analysis, IR, 1H, 13C, or 31P NMR spectroscopy, and X-ray crystallography (1-12). In all of the complexes, thiosemicarbazones are acting as neutral S-donor ligands in eta()S or mu2-S bonding modes. The Cu...Cu separations in the Cu(mu2-X)2Cu and Cu(mu2-S)2Cu cores lie in the ranges 2.981(1)-3.2247(6) and 2.813(1)-3.2329(8) Angstroms, respectively. The geometry around each Cu center in monomers and dimers may be treated as distorted tetrahedral. Ab initio density functional theory calculations on model monomeric and dimeric complexes of the simplest thiosemicarbazone [H2C=N-NH-C(S)-NH2, Htsc] have revealed that monomers and halogen-bridged dimers have similar stability and that sulfur-bridged dimers are stable only when halogen atoms are engaged in hydrogen bonding with the solvent of crystallization or H2O molecules.
卤化亚铜（I）与一系列硫代氨基脲配体（Htsc）在乙腈中，于三苯基膦（Ph(3)P）存在下反应，生成了三种类型的配合物：（i）单体，[CuX(η1-S-Htsc)(Ph3P)2] [X, Htsc = I (1)、Br (2)、苯甲醛硫代氨基脲（Hbtsc）；I (5)、Br (6)、Cl (7)、吡啶 - 2 - 甲醛硫代氨基脲（Hpytsc）]，（ii）卤素桥联二聚体，[Cu2(μ2-X)2(η1-S-Htsc)2(Ph3P)2] [X, Htsc = Br (3)、Hbtsc；I (8)、呋喃 - 2 - 甲醛硫代氨基脲（Hftsc）；I (11)、噻吩 - 2 - 甲醛硫代氨基脲（Httsc）]，以及（iii）硫桥联二聚体，[Cu2X2(μ2-S-Htsc)2(Ph3P)2] [X, Htsc = Cl (4)、Hbtsc；Br (9)、Cl (10)、吡咯 - 2 - 甲醛硫代氨基脲（Hptsc）；Br (12)、Httsc]。所有这些配合物均通过元素分析、红外光谱、1H、13C或31P核磁共振光谱以及X射线晶体学（1 - 12）进行了表征。在所有配合物中，硫代氨基脲以η()S或μ2-S键合模式作为中性S供体配体。Cu(μ2-X)2Cu和Cu(μ2-S)2Cu核中的Cu...Cu间距分别在2.981(1) - 3.2247(6)和2.813(1) - 3.2329(8)埃范围内。单体和二聚体中每个Cu中心周围的几何形状可视为扭曲的四面体。对最简单硫代氨基脲[H2C=N-NH-C(S)-NH2, Htsc] 的模型单体和二聚体配合物进行的从头算密度泛函理论计算表明，单体和卤素桥联二聚体具有相似的稳定性，并且仅当卤素原子与结晶溶剂或H2O分子形成氢键时，硫桥联二聚体才稳定。
